Development of photographic silver halide material

ABSTRACT

A PHOTOGRAPHIC DEVELOPING METHOD IS DESCRIBED WHICH COMPRISES DEVELOPING AN EXPOSED SILVER HALIDE EMULSION LAYER OF A PHOTOGRAPHIC MATERIAL WITH AN AQUEOUS ALKALINE COMPOSITION IN THE PRESENCE OF A HYDROXYLAMINE DEVELOPING AGENT AND A BIS(PYRIDONE)AZINE OR SALT THEREOF SUBSTITUTED IN THE 1-POSITIONS BY THE SAME OR A DIFFERENT ALKYL OR ARALKYL GROUP. THE BIS(PYRIDONE)AZINE COMPOUND EXHIBITS A SUPER-ADDITIVE DEVELOPING EFFECT UPON THE HYDROXYLAMINE OR DERIVATIVE THEREOF.

United States Patent 3,749,575 DEVELOPMENT OF PHOTOGRAPHIC SILVER HALIDE MATERIAL Jozef Frans Willems, Wilrijk, Belgium, assignor to Gevaert-Agfa N.V., Mortsel, Belgium No Drawing. Filed Oct. 7, 1970, Ser. No. 78,915 Int. Cl. G03c 5/30, 5/54 US. Cl. 9666.3 6 Claims ABSTRACT OF THE DISCLOSURE A photographic developing method is described which comprises developing an exposd silver halide emulsion layer of a photographic material with an aqueous alkaline composition in the presence of a hydroxylamine developing agent and a bis(pyridone)azine or salt thereof substituted in the l-positions by the same or a different alkyl or aralkyl group. The bis(pyridone)azine compound exhibits a super-additive developing eifect upon the hydroxylamine or derivative thereof.

This invention relates to the development of photo-' graphic materials containing exposed silver halide, to new developing combinations and to photographic materials and solutions containing such combinations.

It is known that certain chemical compounds, which used alone are poor developers for photographic silver halide emulsions, become much more effective when used in conjunction with other developers, the effect being known as superadditivity.

In the United Kingdom patent specification 1,154,385 filed Nov. 4, 1966 by Gevaert-Agfa N.V., bis(pyridone) azines have been described for use as superadditive developing agents in conjunction with anionic developing agents such as hydroquinone, derivatives of hydroquinone and ascorbic acid, the ionized forms of which in alkaline medium carry two or more negative charges.

It has now been found that these bis(pyridone)azine compounds also exhibit a superadditive character when used in conjunction with hydroxylamine and derivatives thereof. 7

The use as silver halide developing agents of hydroxylamine and derivatives thereof, of which the oxidation products have the favourable property of leaving no residual stain in the silver image obtained has been disclosed amongst others in United States patent specification 2,857,276 of Edwin H. Land and Helen J. Tracy issued Oct. 21, 1958. Hydroxylamine itself and the monoalkylhydroxylamines are less suitable because they can give rise to fog but the N,N-dialkylhydroxylamines such as N,N-diethylhydroxylamine and the heterocyclic N-hydroxylamines such as N-hydroxymorpholine, N-hydroxypiperidine and N-hydroxypyrrolidine disclosed in the above United States patent specification are particularly suitable. Other hydroxylamine derivatives that have been proposed for use as silver halide developing agents and of which the development activity is higher than that of the N,N- dialkyl hydroxylamines include for example aminoalkyl hydroxylamines, more especially N,N-dialkylhydroxlamines having in at least one of the N-alkyl groups an intralinear amino nitrogen atom, either cyclic or acyclic, examples of which can be found in United States patent specification 3,287,125 of Milton Green, Adnan A. Sayigh and Henri Ulrich, issued Nov. 22, 1966, alkoxyhydroxylamines, more especially N,N-dialkylhydroxylamines of which at least one of the N-alkyl groups is substituted by alkoxy or alkoxyalkoxy, examples of which can be found in United States patent specification 3,293,034 of Milton Green, Adnan A. Sayigh and Henri Ulrich, issued Dec. 20, 1966, and sulphone hydroxylamines, more especially 3,749,575 Patented July 31, 1973 N,N-dialkylhydroxylamines having in at least one of the N-alkyl groups an intralinear sulphonyl (-SO group, examples of which can be found in United States Patent 3,287,124 of Milton Green, Adnan A. Sayigh and Henri Ulrich, issued Nov. 22, 1966. Further, N,N-dialkylhydroxylamines having in at least one of the N-alkyl groups a quaternary ammonium group either cyclic 0r acyclic which excell by their high development activity have been proposed for use as silver halide developing agents in the application Ser. No. 78,916 filed on even date herewith for Novel Photographic Developers.

The bis(pyridone)azine compounds having a superadditive development effect with hydroxylamine developing agents are bis(pyridone)azines substituted in the l-positions by the same or different radical selected from alkyl including substituted alkyl and aralkyl including substituted aralkyl, or such an azine the pyridone nuclei of which are further substituted.

The bis(pyridone)azines of use in the superadditive developing combinations according to the present invention correspond more particularly to the following general formula:

each of R and R the same or diiferent, represents alkyl including substituted alkyl, or aralkyl including substituted aralkyl e.g. alkyl or aralkyl substituted by halogen, hydroxy, alkoxy, sulpho, amino, carbamoyl, and sulphamoyl,

each of n and n, the same or different, represents 0 or 1,

and

each of Z and Z the same or different, represents the atoms necessary to close a pyridone nucleus including a substituted pyridone nucleus, e.g. pyridone substituted by alkyl, halogen, hydroxy, alkoxy, amino, monoalkylamino, dialkylamiuo, sulphonamido and carbonamido.

The bis (pyridone) azines of use according to the present invention can be applied in the form of free bases as well as in the form of their salts.

The following are exemplary bis(pyridone)azines of use according to the present invention.

The bis(pyridone)azine compounds of use according to the present invention can be prepared as described in the United Kingdom patent specification 1,154,385, filed Nov. 4, 1966 by Gevaert-Agfa N.V. I

In accordance with the present invention there is provided a process of making photographic records which comprises treating a photographic material having layers containing developable silver salts with an aqueous alkaline solution in the presence of a hydroxylamine developing agent and a bis(pyridone)azine compound as described above. The invention also includes developer compositions comprising in addition to a hydroxylamine developing agent, a bis(pyridone)azine compound as described. By hydroxylamine developing agent it is intended to embrace hydroxylamine itself as well as derivatives thereof as described above. The bis(pyridone)azines of use according to the present invention may be added to the developing bath or to the emulsion or to both simultaneously, the developing bath being preferred however.

Developer compositions that comprise the superadditive developing agents according to the present invention may comprise in addition thereto any of the common ingredients employed in developing compositions e.g. alkalies such as sodium hydroxide, potassium hydroxide, sodium carbonate, trisodium phosphate, etc., silver halide solvents such as sodium thiosulphate, sodium thiocyanate or cyclic imides such as barbiturates and uracils, preservatives such as sulphites, bisulphites, metabisulphites and acids such as boric acid and citric acid. Further the developer composition may comprise potassium bromide and water-softening agents such as polyphosphates and derivatives of ethylene diamine tetraacetic acid, antifoggants such as benzotriazole, S-nitro-benzotriazole and 6-nitrobenzimidiazole and wetting agents as well as other compounds known in the photographic development technique such as development restrainers and development accelerators.

The ratio of hydroxylamine developing agent to bis- (pyridine) azine compound used in the present invention can be chosen in such a way that the combination is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having highly sensitive silver bromo-iodide emulsion layers. This ratio may vary within wide limits and also depends on the particular bydroxylamine developing agent used. :In most cases the ratio is chosen in such a way that the amount of the hydroxylamine developing agent strongly outweighs the his (pyridone) azine compound.

-A strong super additive effect is obtained by using an amount of 0.05 to 10 mmoles preferably 0.3 to 6 millimoles of bis(pyridone)azine to an amount of 10 to 100 mmoles of hydroxylamine developing agent, per litre of developing composition. Of course larger amounts of said bis(pyridone)azine compounds can be used, although the superadditive effect obtained with higher concentrations is not more considerable.

The novel combination of developing agents of the invention may be used in conventional or wet development of silver halide emulsions, in diffusion transfer processes, both dye and silver, in such photographic processes known as stabilization processing wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print, etc.

In difiusion transfer processes as is well known in the art, an exposed silver halide emulsion is treated with a liquid processing composition while in superposed relationship with an image-receiving material. By this treatment the exposed silver halide is developed to silver and the unexposed silver halide is converted into a complex silver salt which is transferred to the image-receiving material and there reduced to silver to form a positive print. The processing composition normally includes a silver halide solvent, such as sodium thiosulphate, sodium thiocyanate and cyclic imides such as barbiturates or uracils, which form with silver halide a soluble complex as is well known in the art of forming silver images by transfer, and may also include a film-forming material such as sodium carboxymethylcellulose and hydroxyethylcellulose, starch or gum for increasing the viscosity of the composition as, for instance, in the case of incarnera silver complex diffusion transfer processing. In stabilisation processing the time-consuming fixing and washing operations are eliminated in order to produce the photographic record in the least possible time, by converting after development, with the aid of stabilizing agents such as ammonium thiocyanate, the unexposed and undeveloped silver halide of the photographic emulsion into colourless light-insensitive compounds that need not be removed by washing.

The developing agents of use according to the invention may be employed in solution or they may be initially incorporated in a layer of the photosensitive material, e.g. a silver halide emulsion layer or other colloid layer in water-permeable relationship therewith. In silver complex diffusion transfer processes they may also be incorporated in a layer of the image-receiving material which, during processing, is in superposed relationship with the photosensitive silver halide material.

The following examples illustrate the favourable superadditive effect of the compounds of use according to the invention on the development by hydroxylamine and derivatives thereof.

EXAMPLE 1 The other strip is developed in a bath A having the same composition of bath A biit containing moreover 89 mg. (0.31 mmole) of Compound 5.

The densities obtained are listed in the table below.

TABLE Densities obtained after a developing time of- Developing bath 0 sec. 20 sec. 1 min. 3 min. 5 min. 33; 2211;131:1213: 8:82 3:32 1: it 9:32 iii? EXAMPLE 2 This example is analogous to Example 1, with the only difference that now developing baths B and B9 are used which only differ from baths A and A in that the hydroxylamine hydrochloride has been replaced by 0.06

mole of N-methylhydroxylamine hydrochloride.

The following results are attained.

TAB LE Densities obtained after a developing time of- Developlng bath 0 sec. 20 sec. 1 min. 3 min. 5 min.

Bath B1 0. 05 0. 05 0. 07 0 60 1. 07 Bath B2 o. 04 0. 35 0. as if 53 2.19

EXAMPLE 3 This example is analogous to Example 1, with the difference that now developing baths C and C are used which only differ from baths A and A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of N,N-diethylhydroxylamine oxalate and that a 5 bath C is used which differs from bath C in that the 0.31 mmole of compound 5 is replaced by 0.31 mmole of Compound 13.

The following results are attained.

TABLE Densities obtained after a developing time of Developing bath sec. 20 sec. 1 min. 3 min. min- Bath 01 0. 04 0. 04 0. 04 0. 07 0. 37 Bath C2 0. 04 0. 24 0. 66 1. 45 2. 17 Bath 0 0. 04 0. 04 0. 05 0. 51 1. 78

EXAMPLE 4 This example is analogous to Example 1, with the only difference that now developing baths D and D are used which only differ from baths A and A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of N-methyl-N-(2-hydroxy-3-diethylaminopropyl) hydroxylamine.

This example in analogous to Example 1, with the only difference that now developing baths E and B are used which only differ from baths A and A in that the hydroxylamine hydrochloride has been replaced by 0.0 6 mole of the hydroxylamine derivative with formula:

according to the application Ser. No. 78,916 filed on even date herewith for Novel Photographic Developers referred to above.

The following results are obtained.

TABLE Densities obtained after a developing time of- Developing bath 0 sec. 20 sec. 1 min. 3 min. 5 min.

Bath E1 0. 04 0. 04 0. 20 1. 29 2.08 Bath E2 0. 04 0.52 1. 28 2. 37 3 EXAMPLE 6 This example is analogous to Example 1, with the only difference that now developing baths F and F are used which only differ from baths A and A in that the hydroxylamine hydrochloride has been replaced by 0.05 mole of the hydroxylamine derivative with formula:

6 EXAMPLE 7 A photosensitive element was prepared comprising on a paper support a silver bromoiodide emulsion layer containing per kg. an amount of silver halide corresponding to g. of silver nitrate.

After exposure, the photosensitive element and an image-receiving element, which comprises a silver receptive layer containing development nuclei dispersed in a matrix of colloidal silica coated on a water-impervious support according to the practice described in the United States patent specification 2,823,122 of Edwin H. Land issued Feb. 11, 1958, were advanced in superposed relationship between a pair of pressure applying rollers to spread between them in a thin layer the following processing composition:

waterl00 ml.

sodium carboXymethylcellu1ose-5 g.

sodium hydroxide-45 g.

uracil-11.25 g.

30% ammonium hydroxide-3.5 ml. N,N-diethylhydroxylamine oxalate0.06- mole 1-phenyl-2-tetrazoline-5-thione0.2 g. compound 5-89 mg.

After a contact period of 36 seconds, the emulsion together with the layer of processing liquid was stripped from the image-receiving element to uncover the positive print.

When using a same developing composition but comprising no compound 5 the density of the positive print obtained was markedly lower. Moreover, in the presence of compound 5 better quality transfer images are obtained at lower illumination levels than is the case when using N,N-diethylhydroxylamine alone.

I claim:

1. Photographic developing method which comprises developing an exposed silver halide emulsion layer of a photographic material with an aqueous alkaline composition comprising a hydroxylamine developing agent and a his (pyridone)azine substituted in the l-positions by the same or different alkyl or aralkyl group, or salt thereof.

2. Photographic developing method according to claim 1, wherein said bis(pyridone)azine corresponds to the formula:

CzHs H oz ti according to the application Ser. No. 78,916 filed on even improvement wherein the process includes the step of date herewith for Novel Photographic Developers referred to above.

The following results are attained.

TABLE developing an exposed silver halide emulsion layer of a photographic material with an aqueous alkaline composition comprising a hydroxylamine developing agent and a bis(pyridone)azine substituted in the one-position by the same or different alkyl or aralkyl group, or salt thereof.

4. Photographic developing method according to claim 1, wherein said hydroxylarnine developing agent and said bis (pyridone)azine are both present in the said aqueous composition.

5. Photographic developing composition for developing an exposed silver halide emulsion layer of a photographic material comprising in aqueous alkaline solution in addition to a hydroxylamine developing agent a bis(pyridone)azine substituted in the l-positions by the same or different alkyl or aralkyl group, or salt thereof.

6. Photographic developing composition according to claim 5 wherein said bis(pyridone)azine corresponds to the formula:

wherein:

each of R and R (the same or different) stands for an alkyl group or aralkyl group,

each of it and n, the same or different, represents 0 References Cited UNITED STATES PATENTS 8/ 1966 Ramsay 9666 12/ 1970 Morse 96-29 2/ 1971 Willems 96-66 NORMAN G. T ORCHIN, Primary Examiner A. T. SURO PICO, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 749, 575 Dated July 31 1973 Inventor(s) Jozef Frans WILLEMS It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, in the heading, add the claim for priority as follows:

-Claims Priority of Great Britain Application No. 52. 566/69 filed October 27, 1969 Column 1, line 13, "exposd" should read exposed Column 3,

line 26, "(pyridine)" should read (pyridone) Column 3, line 54, after "processes" insert a comma Signed and sealed this 16th day of July 1971+.

(SEAL) Attest: v

McCOY M. GIBSON, JR. 6 C. MARSHALL DANN Attesting Officer Commissioner of Patents USCOMM-DC 60376-1 69 u.s. GOVERNMENT PRINTING orncs: "ID 0-505-334, 

